Thermoplastic resin silicone composite shaped article

ABSTRACT

A thermoplastic resin-silicone composite shaped article comprising (a) a shaped article of a thermoplastic resin selected from the group consisting of olefin resins, urethane resins and styrene resins and (b) a cured layer of an additional polymerization type silicone composition adhering to the one or both surfaces of the shaped article of a thermoplastic resin. To the surface of the above shaped article of a thermoplastic resin to which the above cured layer of an additionl polymerization type silicone composition does not adhere, there may adhere another cured layer of the above addition polymerization type silicone composition. To either or both of these cured layers, there may further adhere a layer of the above thermoplastic resin, other thermoplastic resin, a silicone rubber, a silicone resin, glass, ceramics or a metal.

This is a division of application Ser. No. 917,194 filed Oct. 9, 1986which is a division of Ser. No. 675,997 filed Nov. 29, 1984, now U.S.Pat. No. 4,686,124.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a thermoplastic resin-silicone compositeshaped article comprising a layer of a thermoplastic resin and a curedlayer of an addition polymerization type silicone composition in theform of a laminate of these layers. The present invention is to providenew and useful medical devices made from the above composite shapedarticle, such as blood bag, medical tube and the like.

2. Description of the Prior Art

In general, silicone polymers are superior in thrombus resistance andhistocompatibility and have been expected as a medical material.However, they are used only in a limited amount in medical field becauseof their high cost and low mechanical strength.

Of thermoplastic resins being used in medical applications, soft vinylchloride resins, by the addition of a plasticizer, a high molecularelastomer or the like, have flexibility, excel in transparency, and aregood in adhesion and processability by high frequency or other method.However, the soft vinyl chloride resins have a hygienic problem ofdissolution cf plasticizer and the like into an adjacent liquid and,moreover, are inferior in thrombus resistance, histocompatibility, etc.

Olefin resins, particularly, polyethylene, polypropylene andethylene-propylene copolymers are inexpensive and are superior intoughness and rigidity. However, they are insufficient in flexibilityand thrombus resistance.

Urethane resins excel in toughness and flexibility; however most of themare low in rigidity and all urethane resins except segmented ones areinsufficient in thrombus resistance.

Styrene resins excel in transparency and rigidity and are widely used inmedical utencils, food packaging, etc. However, they are insufficient inflexibility and poor in thrombus resistance.

Thus, silicone polymers and various thermoplastic resins now in use inmedical applications each have strong points and weak points. Therefore,various attempts have been made of using two or more of these materialsas one composite material.

Conventional silicone rubbers and resins are generally inactive and poorin adhesivity. Their adhesion to other resins is not sufficient even ifthey contain polar group-containing components present in condensationtype RTV silicones or in so-called self-adhering silicones disclosed inJapanese Patent Application Kokai (Laid-Open) No. 24258/77, etc.

With respect to vinyl chloride resins, particularly, soft vinyl chlorideresins, it has been generally thought that their strong adhesion tosilicone polymers is difficult due to the effect- of additives containedin the vinyl chloride resins such as a stabilizer, a plasticizer and thelike. In order to overcome this drawback, there were proposed variousmethods in which the surface of a soft vinyl chloride resin is treated,for example, with a primer and then a silicone layer is formed thereon.However, these methods had drawbacks in that (a) the process arecomplex, (b) many primers use a solvent such as ethyl acetate, tolueneor the like and the solvent may remain partly and (c) the adhesionbetween the vinyl chloride resin and the silicone layer causesseparation with the lapse of time.

Japanese Patent Application Kokai (Laid-Open) No. 156083/79, etc.proposed a method wherein the surface of a vinyl chloride resin issubjected to low temperature plasma treatment and then thereon is formeda cured layer of a condensation type RTV silicone. Japanese PatentApplication Kokai (Laid-Open) No. 32773/83 proposed the modification ofa vinyl chloride resin material in which the surface of the vinylchloride resin material is subjected to plasma treatment or the like toform a cured layer and then thereon is formed a silicone resin layercomposed of a dimethylpolysiloxane or an alkyl group-modifieddimethylpolysiloxane. From these methods, it is clear that a siliconeresin can be allowed to adhere to the surface of a vinyl chloride resin.However, it is difficult to subject the inner surface of a smalldiameter tube or a long tube made of a vinyl chloride resin material toa complete low temperature plasma treatment to form a cured layer.

Olefin resins are crystalline resins of no polarity and are hardlysoluble in solvents. Therefore, their adhesion to metals or plastics isvery difficult. Their strong adhesion particularly to silicones havebeen thought to be almost impossible.

Hence, in order to obtain adhesion between an olefin resin and asilicone, there were made various attempts in which (1) the surfaces ofthe olefin resin and the silicone are each subjected to a physicaltreatment such as corona discharge or the like or to a chemicaltreatment by a bichromic acid-sulfuric acid mixture or the like to causesurface oxidation and form an oxide film containing polar groups such ascarbonyl group and the like and then (2) these two treated surfaces areallowed to adhere to each other by the use of an adhesive ofepoxy-polyamide, nitrile rubber, isocyanate, cyanoacrylate or othertype. In any of these attempts, however, no practically usable adhesioncould be achieved.

Methods for adhesion between various base materials and silicones viavarious primers are described in Japanese Patent Application Kokai(Laid-Open) No. 23667/82, Japanese Patent Application Kokai (Laid-Open)No. 162711/82, etc. However, no reporting has been made yet regardingstrong adhesion between thermoplastic resins such as urethane resins andstyrene resins and addition polymerization type silicones withoutrequiring the above primer treatment which is complicated.

Thus, use of composite materials between thermoplastic resins andsilicone polymers have been strongly desired; however no such materialswhich can be put into practical applications have been available.

With respect to soft vinyl chloride resins which contain a plasticizer,etc., dissolution of the plasticizer, etc. into an adjacent liquid hasbeen a concerned matter. However, no effective method for overcoming theproblem has been established yet. For example, in Japanese PatentApplication Kokai (Laid-Open) No. 116469/81, it is reported thatplasticizer dissolution can be reduced by subjecting the surface of asoft vinyl chloride resin to low temperature plasma treatment. However,the plasma treatment is extremely difficult for shaped articles of longtube configuration particularly with a small inner diameter. Also, it issaid that the plasma treatment deteriorates the biocompatibility of softvinyl chloride resins. Therefore, the plasma treatment for soft vinylchloride resins has not been put into practical application.

SUMMARY OF THE INVENTION

The object of this invention is to produce from (a) thermoplastic resins(soft vinyl chloride resins, olefin resins, urethane resins and styreneresins) which are in wide use as medical devices or packaging materialsfor several excellent characteristics despite some weak points and (b)silicone rubbers which are expensive and insufficient in strength butsuperior in biocompatibility, etc., a composite shaped article betweenthe materials (a) and (b) in which the strong points of the materials(a) and (b) are utilized and their weak points are made up for and aresuitable for medical applications.

The present inventors made extensive study with a view to obtain anexcellent composite shaped article between (a) thermoplastic resins(soft vinyl chloride resins, olefin resins, urethane resins and styreneresins) having various excellent characteristics and (b) siliconessuperior in biocompatibility, etc. As a result, it was found thatsurprisingly there are combinations of resins in which a thermoplasticresin of vinyl chloride, olefin, urethane or styrene type and a siliconecan strongly adhere to each other. By further continuing the abovestudy, a useful composite shaped article of the present invention hasbeen completed.

According to the present invention, there is provided a thermoplasticresin-silicone composite shaped article comprising (a) a shaped articleof a thermoplastic resin selected from the group consisting of softvinyl chloride resins, olefin resins, urethane resins and styrene resins(the resin is hereinafter referred simply to as a thermoplastic resin)and (b) a cured layer or cured layers or an addition polymerization typesilicone composition adhering to at least one surface of said shapedarticle. The present invention further provides a multilayer laminatecomprising (a) at least two layers of the above mentioned shaped articleof a thermoplastic resin and (b) at least one cured layer of an additionpolymerization type silicone composition, wherein (1) said layers of theshaped article of a thermoplastic resin adhere to each other throughsaid cured layer of an addition polymerization type siliconecomposition, (2) the outermost layers of said laminate are the layer (s)of said shaped article of a thermoplastic resin and/or the curedlayer(s) of said addition polymerization type silicone composition, and(3), when the outermost layer(s) of said laminate is (are) the curedlayer(s) of said addition polymerization type silicone composition, alayer (layers) of a material selected from the group consisting ofthermoplastic resins other than said thermoplastic resin, siliconerubbers, silicone resins, glass, ceramics and metals may further adhereto the outermost layer(s). More specifically, the present inventionprovides a multilayer blood bag consisting of at least two layers of athermoplastic resin layer and a cured layer of an additionpolymerization type silicone composition wherein the cured layer of anaddition polymerization type silicone composition comes into directcontact with blood; a catheter tube with a balloon, characterized inthat the catheter tube and the balloon are made from a same or differentthermoplastic resin or a silicone rubber and, at the balloon-fixingportion of the catheter, are laminated into one integral body with anaddition polymerization type silicone composition; and a compositeshaped article wherein a soft vinyl chloride resin an additionpolymerization type silicone and an ethylene-vinyl alcohol copolymer,or, a soft vinyl chloride resin, an addition polymerization typesilicone, an ethylene-vinyl alcohol copolymer and an additionpolymerization type silicone are laminated in this order to greatlyreduce the dissolution of a plasticizer contained in the soft vinylchloride resin into a liquid which will come into contact with thecomposite shaped article.

DETAILED DESCRIPTION OF THE INVENTION

In the present invention, the soft vinyl chloride resins arecompositions each comprising (1) a main component of a vinyl homopolymeror a copolymer composed essentially of vinyl chloride such as a vinylchloride-ethylene copolymer, a vinyl chloride-vinyl acetate copolymer, avinyl chloride-ethylene-vinyl acetate terpolymer, a vinylchloride-(meth)acrylate copolymer, a vinyl chloride-urethane copolymeror the like, (2) a plasticizer which imparts flexibility to the maincomponent and (3) other components.

As the plasticizer, there can be used, for example, aliphatic dibasicacid esters (e.g. dioctyl phthalate, dioctyl adipate, dibutyl sebacate),polyester type plasticizers, epoxidized soybean oil, epoxidized linseedoil, etc. Use of these plasticizers in 100 phr by weight or morerelative to the resin tends to reduce the bonding strength of the softvinyl chloride resin to an addition polymerization type siliconecomposition. When the amount of a plasticizer added is less than 100 phrby weight, a fairly wide range of vinyl chloride resins from hard typeto soft type can be practically used. Therefore, a past general conceptthat adhesion between a soft vinyl chloride resin and a silicone isextremely difficult has been overthrown by the present invention. Ofthese plasticizers, phthalic acid esters such as dioctyl phthalate,epoxidized soybean oil and epoxidized linseed oil can retain the bondingstrength of the soft vinyl chloride resin fairly well and therefore theyare particularly preferred plasticizers. Besides, non-liquid highmolecular substances capable of imparting flexibility to vinyl chlorideresins, such as urethane polymers, ethylene-vinyl acetate copolymers andthe like can also be used as plasticizers.

Further, as a stabilizer for imparting heat resistance and heatstability, there can be used in the soft vinyl chloride resin of thepresent invention (1) metal soaps composed of a metal such as Ca, Zn,Pb, Ba, Mg, Al or the like and a higher fatty acid such as stearic acid,(2) organometal and inorganic metal stabilizers of the above metals, (3)organotin type stabilizers, (4) organic silicon type stabilizers, and(5) ester type stabilizers such as butyl stearate and the like. Ofthese, there are preferred metal soaps such as Ca stearate, Zn stearate,Pb stearate, Ba stearate and the like as well as organometal andinorganic metal stabilizers of the above metals. Organotin typestabilizers are effective only when a plasticizer is used in a smallamount, and they may reduce the bonding strength between a vinylchloride resin and an addition polymerization type silicone compositionwhen the plasticizer is contained in 50 phr or more. Ester typestabilizers (e.g. butyl stearate) and phosphoric acid type stabilizersinhibit the curing of a silicone composition when they are used incombination, and therefore, these two types of stabilizers cannot beused in combination.

In the vinyl chloride resin, there can also be used additives such as anultraviolet inhibitor, a pigment, an antistatic agent, an X-ray contrastmedium and the like. As a lubricant for imparting lubricity, there canbe used higher fatty acids, higher alcohols, low molecularpolyethylenes, amides, esters and the like. Higher fatty acids aslubricant, such as stearic acid and the like tend to plate out on thesurface of the vinyl chloride resin, and therefore, their amounts mustbe restricted. Lubricants such as stearic acid and the like are usedpreferably in an amount of 0.5 phr or less, particularly when they areused in combination with barium sulfate employed in medical field as anX-ray contrast medium, bismuth subcarbonate, etc.

As described above, widely known components are used in the soft vinylchloride resin of the present invention.

In the present invention, the olefin resins are low densitypolyethylenes, medium density polyethylenes, high density polyethyleneslinear low density polyethylenes, polypropylenes, ethylene-propyleneblock copolymers, ethylene-propylene random copolymers,ethylene-propylene-diene terpolymers, ethylene-vinyl acetate copolymers,ethylene-vinyl alcohol copolymers, ionomer resins, polybutadienes,butadiene copolymers, etc. They are used as a single polymer or amixture of two or more. Those polymers having a relatively large amountof unsaturated double bonds within the molecules are preferred.Polyethylenes originally have a molecular structure of CH₂ straightchain as shown in the formula (1). There are many cases that theycontain in their molecules unsaturated double bonds as shown in theformulas (2), (3) and (4), depending upon the polymerization conditions,etc. As is well known, the presence of vinyl group at the molecular endsis confirmed even in high density polyethylenes by infraredspectrophotometry. It is preferable that the olefin resins of thepresent invention contain as many unsaturated double bonds as possiblein their molecules. ##STR1##

In the present invention, the urethane resins refer to resins havingurethane bonds such as polyurethane resins, thermoplastic polyurethaneelastomers and the like as well as to urethane copolymers such asurethanesilicone copolymers and the like. Further, there are includedpolyurethanes having crosslinked structures such as room temperaturesetting type polyurethanes and the like.

In the present invention, the styrene resins refer to polystyrenes,styrene copolymers (e.g. styrene-butadiene copolymers,styrene-acrylonitrile copolymers, styrene-methyl methacrylatecopolymers, acrylonitrile butadiene-styrene terpolymers), polymers ofstyrene derivatives such as methylstyrene, dichlorostyrene and the like,and blends comprising essentially a polystyrene such as high impactpolystyrene. It is generally thought that styrene polymerizationreaction proceeds similarly to the chain reaction of a monomer having avinyl group. Therefore, it is thought that styrene resins containunsaturated double bonds as vinyl chloride resins do. The presence of asmany unsaturated double bonds as possible is preferred.

In the present invention, the addition polymerization type siliconecompositions are compositions each consisting of (a) a polysiloxanehaving vinyl groups represented by the formula (5), ##STR2## wherein R₁,R₂, R₃ and R₄ may be same or different and are each a monovalenthydrocarbon group having 6 or less carbon atoms and m is a positiveinteger, (b) an organohydrogenpolysiloxane represented by the formula(6), ##STR3## wherein R₅, R₇, R₈, R₉ and R₁₀ may be same or differentand are each a monovalent hydrocarbon group having 6 or less carbonatoms, two R₆ 's each are a hydrogen atom or a same or differentmonovalent hydrocarbon group having 3 or less carbon atoms, n is aninteger of 2 to 100 and l is an integer of 0 to 100, and (c) aninorganic substance as a reinforcing component such as silica or thelike. The compositions can be converted into a solid elastomer whensubjected to addition polymerization in the presence of a platinum typecatalyst.

The present inventors found that an addition polymerization typesilicone composition can have a very high adhesion strength toward avinyl chloride resin if the silicone composition contains anorganohydrogenpolysiloxane represented by the formula (6) having atleast two hydrogen atoms directly bonded to silicon atoms in eachmolecule, in an amount enough to provide one to six such hydrogen atomsper one vinyl group in the formula (5).

A similarly high bonding strength can also be obtained by a siliconecomposition containing at least one compound selected from componentscontained in so-called self-adhering silicone rubbers, namely, epoxycompounds, carboxylic acid anhydrides, silanes or siloxanes having anacryloxyalkyl group represented by the general formula (7), ##STR4##wherein R is CH₃ or a hydrogen atom and n is an integer of 1 to 3, andunsaturated hydrocarbon group-containing oxysilane compounds, if theabove silicone composition contains an organohydrogenpolysiloxanerepresented by the formula (6) having at least two hydrogen atomsdirectly bonded to silicon atoms in each molecule, in an amount enoughto provide one to six such hydrogen atoms per one vinyl group in theformula (5). The presence of these adhesion improvers further enhancesthe bonding strength of an addition polymerization type siliconecomposition.

The strength of the cured layer of an addition polymerization typesilicone composition of the present invention can be enhanced byincorporating into the composition a resinous copolymer containing vinylgroups which is dissolved in components of the formulas (5) and (6). Asone example of such a copolymer, there is an organopolysiloxane obtainedfrom copolymerization of the following formulas (8), (9) and (10),

    (CH.sub.2 =CH)(R.sub.11)(R.sub.12)SiO.sub.0.5              ( 8)

    SiO.sub.2                                                  ( 9)

    (R.sub.13).sub.3 SiO.sub.0.5                               ( 10)

In the above formulas, R_(ll), R₁₂ and R₁₃ may be same or different andare each a monovalent hydrocarbon group having 6 or less carbon atoms.

As described in Japanese Patent Publication Nos. 45098/80 and 33256/78,Japanese Patent Application Kokai (Laid-Open) Nos. 126455/77 and101884/79, U.S. Pat. No. 3,527,655 and other literature references, itis a known fact that compositions between an addition polymerizationtype silicone and other various components adhere strongly to metals,ceramics, glass and such resins as those having polar groups (e.g. epoxyresins, polyesters, polymethyl methacrylate, polycarbonates,polyamides). However, there has hitherto been no reporting that theseaddition polymerization type silicone compositions adhere strongly toresins having no polar group such as soft vinyl chloride resins, olefinresins, styrene resins, urethane resins and the like without using aprimer or the like. Rather, adhesion between a silicone and thesethermoplastic resins has been thought to be extremely difficult.

Thus, it is absolutely necessary in the present invention that, forstrong adhesion to thermoplastic resins, an addition polymerization typesilicone composition contain an organohydrogenpolysiloxane having atleast two hydrogen atoms bonded directly to silicon atoms in eachmolecule, in an amount enough to provide excessive (1 to 6) suchhydrogen atoms per one vinyl group of the silicone composition. However,when the very surface of a thermoplastic resin to which an additionpolymerization type silicone composition is allowed to adhere issubjected beforehand to low temperature plasma treatment, coronadischarge, ultraviolet irradiation or the like, because the surface isgiven polarity by such treatment, the addition polymerization typesilicone composition can contain the above-mentionedorganohydrogenpolysiloxane in a lesser amount, namely, an amount toprovide about 0.8 to 6 hydrogen atoms directly bonding with siliconatoms per one vinyl group of the silicone composition and still asufficient adhesion strength is secured. Also when a thermoplastic resinto which an addition polymerization type silicone composition is allowedto adhere contains 0.1 to 10 parts by weight, relative to 100 parts byweight of the resin, of a thermoplasticity-imparting resin having anumber mean polymerization degree of 3 to 200 and having at least onecarbon-carbon double bond per three polymerization units, theaddition,polymerization type silicone composition can contain theabove-mentioned organohydrogenpolysiloxane in a smaller amount, namely,an amount to provide about 0.8 to 6 hydrogen atoms directly bonded tosilicon atoms per one vinyl group of the silicone composition and stilla sufficient bonding strength is secured.

As the above-mentioned thermoplasticity-imparting resin having C--Cdouble bonds in the molecule, there are mentioned diallyl phthalateprepolymers, polybutadienes, etc. Any thermoplasticity-imparting resincan be used if it has a number mean polymerization degree of 3 to 200and at least one C--C double bond per three polymerization units. Whenthe number mean polymerization degree is less than 3, thethermoplasticity-imparting resin tends to cause plate-out from thesurface of a thermoplastic resin in which it is contained, resulting inreduced adhesivity. When the number mean polymerization degree exceeds200, the compatibility between the thermoplasticity-imparting resin anda thermoplastic resin is reduced.

In the present invention, when a thermoplastic resin contains anorganohydrogenpolysiloxane having at least 30 mole % of anorganohydrogensiloxane unit in an amount of 0.01 to 10 parts by weightrelative to 100 parts by weight of the resin, because the resin containsthe organohydrogensiloxane unit thought to be closely connected withadhesivity between a thermoplastic resin and a silicone, in a sufficientamount, the thermoplastic resin can be allowed to adhere to an additionpolymerization type silicone composition whose component formulation canvary fairly widely, that is, an addition polymerization type siliconecomposition containing an organohydrogenpolysiloxane having at least twohydrogen atoms directly bonded to silicon atoms in each molecule, in anamount to provide 0.6 to 6 such hydrogen atoms per one vinyl group ofthe silicone composition.

As described above, an adhesivity of a thermoplastic resin toward anaddition polymerization type silicone composition can be improved by asurface treatment such as plasma treatment, addition of anorganohydrogenpolysiloxane, or addition of a thermoplasticity-impartingresin having carbon-carbon double bonds. However, even if athermoplastic resin is improved in adhesivity by one of the abovemethods, if the thermoplastic resin contains such substances as impairthe curing of an addition polymerization type silicone composition towhich the thermoplastic resin is allowed to adhere, namely, an organotintype stabilizer and the like, in a relatively large amount, inhibitoryactions of these substances reduce adhesivity between the thermoplasticresin and the silicone composition and obtainment of sufficient adhesionis difficult.

Specific useful applications of the thermoplastic resin-siliconecomposite shaped article of the present invention will be described.

The composite shaped article of the present invention can be used as acatheter wherein the surface of a shaped article of a thermoplasticresin according to the present invention is coated with an additionpolymerization type silicone composition of the present invention, as amembrane for oxygenerators or for gas enrichment wherein a porous orfibrous film composed of a thermoplastic resin of the present inventionis coated with an addition polymerization type silicone composition ofthe present invention, and as a multilayer blood bag wherein one layercoming into direct contact with blood is an addition polymerization typesilicone composition of the present invention and the other layer is athermoplastic resin of the present invention. This blood bag improvesthe drawbacks of conventional blood bags, is tough and transparent, andis superior in long term storage of blood and property ofplatelet-adhering. Also, a composite bag consisting of a polyester,nylon, a thermoplastic resin of the present invention and an additionpolymerization type silicone composition of the present invention can beprovided by the present invention for use as a heat-resistant bag suchas a retort pouch.

Further, there can be provided a catheter tube with a balloon whereinthe catheter tube and the balloon are each made of a same or differentthermoplastic resin or silicone rubber and, at the balloon-fixingportion of the catheter tube, the catheter tube and the balloon arebonded strongly with an addition polymerization type siliconecomposition of the present invention. This catheter tube with a balloonenables wide and flexible selection for material combination of tubemain body and balloon. For example, there can be provided aSengstaken-Blakemore tube wherein a balloon of silicone rubber is fixedto a tube of soft vinyl chloride resin, as well as a dilation catheterwherein a balloon of polyethylene is fixed to a tube of soft vinylchloride resin. These material combinations have not hitherto beenemployed and are novel in the present invention. Thus, the presentinvention can provide various catheter tubes with a balloon for medicaluse. By applying this technique, it becomes possible as necessary that acured layer of an addition polymerization type silicone composition ofthe present invention is provided only at the balloon-fixing portion ofa tube made of an urethane resin, a soft vinyl chloride resin or thelike and, on the cured layer, there is fixed a balloon made of asilicone rubber, with a condensation type RTV silicone.

Furthermore, the present invention can provide a thermoplasticresin-silicone composite shaped article wherein plasticizer dissolutionfrom the soft vinyl chloride resin layer into liquid adjacent to thecomposite article is greatly reduced. This composite shaped article is alaminate of a soft vinyl chloride resin, an addition polymerization typesilicone and an ethylene-vinyl alcohol copolymer or of a soft vinylchloride resin, an addition polymerization type silicone, anethylene-vinyl alcohol copolymer and an addition polymerization typesilicone in this order and is characterized in that the permeation ofplasticizer through the laminate is prevented or suppressed by theethylene-vinyl alcohol copolymer layer.

It is a known fact that ethylene-vinyl alcohol copolymers have anexcellent barrier property for oxygen gas. It is also known, however,that the copolymers are relatively high in moisture uptake and, oncethey have absorbed moisture, the barrier property is greatly reduced.The present inventors found that ethylene-vinyl alcohol copolymers,regardless of whether they are in a dry state or in a moisture-wetstate, are very resistant to the permeation of plasticizers such asdioctyl phthalate and the like. Based on this finding and also on aknowledge that an ethylene-vinyl alcohol copolymer can adhere stronglyto an addition polymerization type silicone, the present invention hasbeen completed.

The above composite shaped article comprises (a) a base layer made of atough and flexible soft vinyl chloride resin, (b) an ethylene-vinylalcohol copolymer layer capable of greatly suppressing the permeation ofa plasticizer from the soft vinyl chloride resin and (c) an outermostlayer made of a silicone rubber or an ethylene-vinyl alcohol copolymer.Hence, the composite shaped article has excellent biocompatibility andcan be very suitably used in medical applications.

The thermoplastic resin-silicone composite shaped article of the presentinvention has wide applications also in various industrial fields. Forexample, soft vinyl chloride resins or polyolefins, for both of which ithas been said that there is no effective adhesive, can have strongadhesion among themselves by the use of an addition polymerization typesilicone composition. This enables connection between industrial pipesmade of the above resins. The resulting connected pipes are included inthe composite shaped article of the present invention. Also, an additionpolymerization type silicone composition can be utilized as asurface-protecting film for thermoplastic substrate materials used inelectronics field. These surface-protected substrate materials are alsoincluded in the composite shaped article of the present invention.

As described above, the composite shaped article of the presentinvention can be widely used in medical field, various industrialfields, etc.

The detailed mechanism of adhesion between a thermoplastic resin and anaddition polymerization type silicone composition in the thermoplasticresin-silicone composite shaped article of the present invention is notclear. As one possible mechanism, it can be surmised that theorganohydrogensiloxane group of the addition polymerization typesilicone composition reacts with the functional group of thethermoplastic resin. This can be surmised also from our finding that ahigher content of the organohydrogensiloxane group gives a higherbonding strength. As the functional group of the thermoplastic resin ofthe present invention, there are considered C--C double bonds such asvinyl group and, in this case, there probably occurs an additionreaction between the organohydrogensiloxane group and the C--C doublebond. As previously desired, it is thought that a fairly large amount ofunsaturated double bonds remains particularly in vinyl chloride resins,olefin resins, styrene resins, etc. With respect to urethane resins, thepresence of C--C double bonds will not be probable. Adhesion of anurethane resin to an addition polymerization type silicone compositionwill be due to a reaction between the urethane bond and theorganohydrogensiloxane group or to an affinity between the polar groupof the urethane resin and the organohydrogensiloxane group.

Thus, the mechanism of adhesion between an addition polymerization typesilicone composition of the present invention and a thermoplastic resinof the present invention has not been thoroughly clarified; however theorganohydrogensiloxane group of the addition polymerization typesilicone composition is surmised to be the most important contribution.

Next, a process for producing the thermoplastic resin-silicone compositeshaped article of the present invention will be described. There is noparticular restriction for this process. A desirable example of theprocess is as follows: That is, on the surface of a thermoplastic resinshaped article of the present invention, there is laminated an additionpolymerization type silicone composition of the present invention or asolution of the composition dissolved in an organic solvent, by a methodsuch as coating, dipping, spraying or the like. Then, this integral bodyis subjected to heat treatment at 40° to 130° C., preferably 80° to 120°C. for 5 min to 10 hr, preferably 10 min to 3 hr, whereby a cured layeris formed on the thermoplastic resin shaped article. Certain kinds ofaddition polymerization type silicone compositions using achloroplatinic acid catalyst can cure in a time period as short as 30sec at 100° C. to form a desired film; however in such a short time, nosufficient adhesion strength can be obtained with thermoplastic resins.Certain other kinds of addition polymerization type siliconecompositions containing a platinum type catalyst can cure in 5 min to 3days at 30° C.; however no sufficient adhesion strength can be obtainedas well. Reasons for these poor bonding strengths will be that, in thesekinds of addition polymerization type silicone compositions, thereaction between their hydrogen atoms directly bonded to silicone atomsand C--C double bonds of the thermoplastic resins is greatly dependentupon the reaction temperature and the reaction time.

The cured layer of the addition polymerization type silicone compositionthus formed adheres very strongly to the surface of the thermoplasticresin shaped article of the present invention. This adhesion does notdeteriorate with the lapse of time and also even after a severetreatment such as autoclave or the like.

EXAMPLE 1

Adhesivities between various thermoplastic resins and various siliconeswere investigated in accordance with JIS K 6301. Each thermoplasticresin was kneaded at 170° to 200° C. for 3 to 5 min by the use of an 8in. roll and then press-molded at 170° to 200° C. for 2 to 7 min toobtain sheets each of 20 mm×50 mm×1 mm. Between two of these sheets,there was placed an addition polymerization type silicone in a thicknessof 1 mm. They were heated at 80° to 110° C. for 60 to 90 min to obtain atest specimen for adhesion test. All test specimens thus obtained weresubjected to 180° peeling test by the use of universal tensile testinginstrument. The results are shown in Table 1.

                  TABLE 1                                                         ______________________________________                                        Unit: kg/cm                                                                                           Comparative                                                         Example   Example                                                             Silicone *2                                                                     Addition    Condensation                                                      polymerization                                                                            type RTV                                          Thermoplastic   type silicone                                                                             silicone                                          resin *1            A       B     C     D                                     ______________________________________                                        Soft vinyl                                                                              A         ⊚ 2.8                                                                  ⊚ 4.0                                                                0.1   0.1                                   chloride resin                                                                          B (Plasma-                                                                              ⊚ 4.0                                                                    --  0.3   0.9                                             treated A)                                                          Olefin resin                                                                            A         ⊚ 2.7                                                                  ⊚ 3.0                                                                0.1   0.1                                             B         ⊚ 2.1                                                                  ⊚ 2.4                                                                0.1   0.1                                   Urethane resin                                                                          A         ⊚ 2.9                                                                  ⊚ 3.9                                                                0.1   0.2                                             B         ⊚ 2.8                                                                  ⊚ 4.0                                                                0.1   0.1                                   Styrene resin                                                                           A         ⊚ 3.1                                                                  ⊚ 3.2                                                                0.2   0.2                                             B         ⊚ 2.9                                                                  ⊚ 3.1                                                                0.1   0.1                                   ______________________________________                                        Note: ⊚ indicates cohesive failure of silicone layers.         *1 Thermoplastic resins:                                                      Soft vinyl chloride resin A                                                   This resin was prepared by adding, to 100 parts                               by weight of a vinyl chloride resin (SX-DH, manufactured                      by SUMITOMO CHEMICAL CO., LTD.), 50 parts by weight of                        dioctyl phthalate, 0.025 part by weight (as metal) of Zn                      stearate, 0.025 part by weight (as metal) of Ca stearate                      and 10 parts by weight of epoxidized soybean oil.                             Soft vinyl chloride resin B                                                   This resin was prepared by subjecting sheets of                               the soft vinyl chloride resin A to low temperature plasma                     treatment under the following conditions. The sheets of                       the soft vinyl chloride resin A were placed in a chamber.                     The chamber inside pressure was made vacuum to 0.05 Torr                      and argon gas was introduced into the chamber at a rate of                    300 ml/min, whereby the chamber inside pressure was made                      at about 0.15 Torr. Then, discharging was allowed to occur                    for 5 min inside the chamber by the use of high frequency                     internal electrodes with a voltage of 700 W applied be-                       tween the electrodes, whereby the surfaces of the soft vinyl                  chloride resin A sheets were subjected to plasma treatment.                   Olefin resin A                                                                A low density polyethylene (SUMIKATHENE F 208,                                manufactured by SUMITOMO CHEMICAL CO., LTD.)                                  Olfein resin B                                                                A polypropylene (SUMITOMO NOBLEN FL-6315, manu-                               factured by SUMITOMO CHEMICAL CO., LTD.)                                      Urethane resin A                                                              A thermoplastic polyurethane (TAKELAC T-895,                                  manufactured by Takeda Chemical Industries, Ltd.)                             Urethane resin B                                                              A segmented polyurethane (Pellethene, manufactured                            by Upjohn Co.)                                                                Styrene resin A                                                               A polystyrene (HH 30, manufactured by Idemitsu                                Petrochemical Co., Ltd.)                                                      Styrene resin B                                                               A polystyrene (HT 50, manufactured by Idemitsu                                Petrochemical Co., Ltd.)                                                      *2 Addition polymerization type silicones:                                    Silicone A                                                                    This silicone was prepared by adding, to 100 parts                            by weight of a dimethylpolysiloxane having dimethylvinyl-                     silyl groups at both ends of the molecular chain and having                   a viscosity of 18,000 cs at 25° C., 5 parts by weight of a             polysiloxane consisting of 10 mole % of a trimethylsiloxane                   unit, 40 mole % of a dimethylsiloxane unit and 50 mole % of                   a methylhydrogensiloxane unit, 20 parts by weight of silica                   and 0.2 part by weight of an isopropyl alcohol solution of                    chloroplatinic acid (1% of platinum in the solution).                         Silicone B                                                                    This silicone was prepared by adding, to 100 parts                            by weight of a dimethylpolysiloxane having dimethylvinyl-                     silyl groups at both ends of the molecular chain and having                   a viscosity of 1,300 cs at 25° C., 15 parts by weight of a             conventionally known copolymer consisting of a (CH.sub.3).sub.3 SiO.sub.0.    unit, a (CH.sub.2CH)(CH.sub.3).sub.2 SiO.sub.0.5 unit and a SiO.sub.2         unit wherein                                                                  the ratio of (1) the sum of the number of (CH.sub.3).sub.3 SiO.sub.0.5        units and the number of (CH.sub.2CH)(CH.sub.3).sub.2 SiO.sub.0.5 units        and (2)                                                                       the number of SiO.sub.2 units is 0.8:1 and the content of                     vinyl group is 0.9% by weight, 25 parts by weight of                          trimethylsilyl-treated silica in the form of aerosol, 5 parts                 by weight of a methylhydrogenpolysiloxane containing about 50                 mole % of a methylhydrogensiloxane unit and having a                          viscosity of 50 cs at 25° C., 0.2 part by weight of an isopropyl       alcohol solution of chloroplatinic acid (1% of platinum in the                solution), 2 parts by weight of an epoxy compound having the                  following structural formula,                                                  ##STR5##                                                                     and 0.5 part by weight of phthalic anhydride.                                 Silicone C                                                                    A condensation type silicone (KE-42-RTV, manu-                                factured by Shin-Etsu Chemical Co., Ltd.)                                     Silicone D                                                                    A condensation type silicone (KE-45-RTV, manu-                                factured by Shin-Etsu Chemical Co., Ltd.)                                 

Adhesivities between various thermoplastic resins containingorganohydrogenpolysiloxanes and commercially available additionpolymerization type liquid silicones were investigated in accordancewith JIS K 6301. Each thermoplastic resin was kneaded at 170° to 200° C.for 3 to 5 min by the use of an 8 in. roll and then press-molded at 160°to 200° C. for 3 min to obtain sheets. Between two of these sheets,there was placed an addition polymerization type silicone in a thicknessof 1 mm. They were heated at 80° to 110° C. for 60 to 90 min to obtain atest specimen for adhesion test. All test specimens thus obtained weresubjected to 180° peeling test by the use of a universal tensile testinginstrument. The results are shown in Table 2.

                  TABLE 2                                                         ______________________________________                                        Unit: kg/cm                                                                                 Silicone                                                                      Commercially available addition                                               polymerization type                                                           liquid silicone                                                                 KE-1910     SE-6720                                                           manufactured                                                                              manufactured                                                      by Shin-Etsu                                                                              by TORAY                                          Thermoplastic   Chemical Co.,                                                                             SILICONE                                          resin *         Ltd.        CO., LTD.                                         ______________________________________                                        Soft vinyl                                                                            1     Comparative                                                                               0.1       0.3                                       chloride      Example                                                         resin   2     Example   ⊚ 3.2                                                                    ⊚ 3.5                        Olefin  1     Comparative                                                                               0.5       0.6                                       resin   2     Example     0.2       0.1                                               3     Example   ⊚ 4.1                                                                    ⊚ 4.3                                4               ⊚ 3.9                                                                    ⊚ 4.2                        Soft vinyl                                                                            3     Comparative                                                                               0.1       0.2                                       chloride      Example     0.1       0.2                                       resin   4     Example   ⊚ 2.1                                                                    ⊚ 2.9                        ______________________________________                                        Note: ⊚ indicates cohesive failure of silicone layers.         * Thermoplastic resin:                                                        Soft vinyl chloride resin 1                                                   This resin was prepared by adding, to 100 parts                               by weight of a vinyl chloride resin (700 D, manufactured by                   TOYO SODA MANUFACTURING CO., LTD.), 0.04 part                                 by weight (as metal) of Zn stearate, 0.02 part by weight                      (as metal) of Ca stearate, 50 parts by weight of dioctyl                      phthalate and 5 parts by weight of epoxidized soybean oil.                    Soft vinyl chloride resin 2                                                   This resin was prepared by adding, to 100 parts by                            weight of the soft vinyl chloride resin 1, 1.5 parts by                       weight of a n-hexane solution containing 70% by weight of                     an organohydrogenpolysiloxane represented by the formula                      (11),                                                                          ##STR6##                     (11)                                            Olfein resin 1                                                                A low density polyethylene (SUMIKATHENE F 101,                                manufactured by SUMITOMO CHEMICAL CO., LTD.)                                  Olfein resin 2                                                                A polypropylene (SUMITOMO NOBLEN S-131, manufactured                          by SUMITOMO CHEMICAL CO., LTD.)                                               Olfein resin 3                                                                This resin was prepared by adding, to 100 parts                               by weight of the olefin resin 1, 1.5 parts by weight of                       a n-hexane solution containing 70% by weight of the organo-                   hydrogenpolysiloxane represented by the formula (11).                         Olefin resin 4                                                                This resin was prepared by adding, to 100 parts by                            weight of the olefin resin 2, 1.5 parts by weight of                          a n-hexane solution containing 70% by weight of the organo-                   hydrogenpolysiloxane represented by the formula (11).                         Soft vinyl chloride resin 3                                                   This resin was prepared by adding, to 100 parts by                            weight of a vinyl chloride resin (700 D, manufactured by                      TOYO SODO MANUFACTURING CO., LTD.), 0.03 part                                 by weight (as metal) of Zn stearate, 0.03 part by weight                      (as metal) of Ca stearate, 40 parts by weight of dioctyl                      phthalate and 10 parts by weight of epoxidized soybean oil.                   Soft vinyl chloride resin 4                                                   This resin was prepared by adding, to 100 parts by                            weight of the soft vinyl chloride resin 3, 0.5 part by                        weight of a diallyl phthalate prepolymer (DAISO DAP L,                        manufactured by OSAKA SODA CO., LTD.)                                     

EXAMPLE 3

The following experiment was conducted to obtain a useful blood bagaccording to the present invention.

Bag 1

A composition consisting of 100 parts by weight of a vinyl chlorideresin, 1.2 parts by weight of a Ca-Zn type composite stabilizer, 42parts by weight of dioctyl phthalate and 8 parts by weight of epoxidizedsoybean oil was subjected to calendering to obtain a sheet of 0.3 mmthickness. One surface of this sheet was coated with a n-hexane solutioncontaining a mixture of 100 parts by weight of a dimethylpolysiloxanehaving vinyl groups at both ends of the molecule and having a viscosityof 18,000 cp, 8 parts by weight of a polysiloxane whosemethylhydrogenpolysiloxane component consists of 10 mole % of atrimethylsiloxane unit, 40 mole % of a dimethylsiloxane unit and 50 mole% of a methylhydrogensiloxane unit, 20 parts by weight of silica and 0.3part by weight of an isopropyl alcohol solution containingchloroplatinic acid (1% platinum in solution), by the doctor blademethod so that the thickness after curing became about 100μ. n-Hexanewas removed and then the coated surface of the above sheet was coveredby a teflon-coated glass-cloth paper. They were placed in a constanttemperature bath at 110° C. for 2 hr for curing. Thereafter, on thesilicone rubber side of the sheet was coated an undiluted additionpolymerization type silicone rubber composition in a thickness of about100μ so that the coated portion formed the fringe of a bag. Two of suchsheets were put together so that respective coated sides faced eachother. Between these two sheets was inserted an extruded tube (6 mm OD×4mm ID) made of the abovementioned soft vinyl chloride resin, as a port.They were heat-cured at 110° C. for 2 hr in molding dies, whereby a Bag1 was obtained.

Bag 2

A vinyl chloride resin sheet was prepared in the same manner as in thecase of Bag 1. On the surface of this sheet which would later form theinner side of a bag, there was coated an addition polymerization typesilicone composition in a thickness of about 50μ, and then the sheet washeated for curing. Thereafter, two of such sheets were put together sothat respective coated sides faced each other and they were subjected tohigh frequency welding at the fringe portion of a bag shape by the useof an ordinary high frequency welding machine.

Bag 3

A resin composition consisting of 100 parts by weight of a polypropylene(SUMITOMO NOBLEN S-131, manufactured by SUMITOMO CHEMICAL CO., LTD.) and20 parts by weight of a polyethylene (SUMIKATHENE F-208, manufactured bySUMITOMO CHEMICAL CO., LTD.) was extruded into a film of 100μ thickness.On one surface of this film, there was coated the additionpolymerization type silicone composition used in the case of Bag 1, in athickness of 100μ. After deaeration in vacuum, the coated surface of thefilm was covered by a teflon-coated glass-cloth paper. They were pressedat 115° C. for 1 hr, whereby a silicone rubber-polyolefin composite filmwas obtained. As in the case of Bag 1, the silicone rubber side of thefilm was coated with an addition polymerization type siliconecomposition so that the coated portion formed the fringe of a bag. Twoof such sheets were put together so that respective coated sides facedeach other. Between these two sheets, there was inserted as a port avinyl chloride resin tube. They were heated at 110° C. for 1.5 hr,whereby a bag was obtained.

Bag 4

Two of the soft vinyl chloride resin sheets used in the case of Bag 1were subjected to high frequency welding, whereby a bag for ComparativeExample was obtained.

The bags thus obtained were subjected to sterilization treatment in anautoclave at 120° C. for 30 min. Into each of these bags, there waspoured 50 ml of a dog's whole blood to which ACD had been added, andeach bag was stored at 4° C. After 1, 4, 8, 24 and 48 hr, the number ofplatelets suspended in the blood was measured for each bag, from which apercentage of platelets decreased was calculated. Retention of red bloodcells was investigated by counting the number of red blood cells in theblood after 24 hr storage.

                  TABLE 3                                                         ______________________________________                                        Number of Platelets Suspended (× 10.sup.4 /mm.sup.3)                               Time of storage at 4° C. hr                                                  0      1     4    8     24   48                              ______________________________________                                        Example  Bag 1   15.9   15.7  15.9 16.5  14.6 12.8                                     Bag 2   15.8   15.8  15.6 15.3  14.2 11.8                                     Bag 3   15.2   16.3  15.1 14.8  15.0 13.4                            Comparative                                                                            Bag 4   16.3   14.4  13.7 11.9  12.7 10.3                            Example                                                                       ______________________________________                                                           Percentage of                                                                 platelets survival                                         ______________________________________                                        Comparative Example (Bag 4)                                                                      After 24 hr 77.9%                                                             After 48 hr 63.2%                                          Example (Bags 1 & 2)                                                                             After 24 hr 90.9%                                                             After 48 hr 77.6%                                          Example (Bag 3)    After 24 hr 98.7%                                                             After 48 hr 88.1%                                          ______________________________________                                    

                  TABLE 4                                                         ______________________________________                                        Retention of Red blood Cells (× 10.sup.4 /mm.sup.3)                                       After 24 Percentage                                                    0 hr   days     of change (%)                                      ______________________________________                                        Example  Bag 1   790      758    -4.0                                                  Bag 2   818      790    -3.4                                                  Bag 3   818      776    -5.3                                         Comparative                                                                            Bag 4   806      620    -23.1                                        Example                                                                       ______________________________________                                    

As is obvious from the Tables 3 and 4, blood bags according to thepresent invention were superior in retentions of both platelets and redblood cells.

The above bags had the physical properties shown in Table 5.

                  TABLE 5                                                         ______________________________________                                                                       Tensile                                                         Peeling strength                                                                            strength                                                Autoclave                                                                             of the sealed of sheet                                                charac- portion       (kg/10 mm                                               teristic                                                                              (kg/20 mm width)                                                                            width)                                         ______________________________________                                        Example                                                                              Bag 1   Good       6.4        7.8                                             Bag 2   Good      11.5        7.2                                             Bag 3   Good       7.2        9.4                                      Com-   Bag 4   Partially 12.3        6.7                                      parative       tacked                                                         Example                                                                       ______________________________________                                    

EXAMPLE 4

In this Example, there was produced a drainage tube used forpercutaneous transhepatic cholangio drainage (PTCD) which is aneffective remedy for obstructive jaundice. In the soft vinyl chlorideresin composition used in Example 1, the amount of diethylhexylphthalate was changed to 30 parts by weight and 100 parts by weight of afine powder of barium sulfate was added as a contrast medium, wherebypellets were prepared. Those pellets were extruded into a tube of 3 mmin outside diameter and 1.5 mm in inside diameter having a fluid passagefor balloon expansion of 0.3 mm in inside diameter. The front end of thetube was made smooth and the front end of the fluid passage for balloonexpansion was sealed. At the balloon-fixing portion of the tube locatedin the vicinity of the front end of the tube, there was opened a sidehole of 0.3 mm in diameter extending to the fluid passage for balloonexpansion. Then, the balloon-fixing portion of the tube was covered witha balloon tube made of a silicone rubber and having an inside diameterof 3.2 mm, a thickness of 0.2 mm and a length of 15 mm. On a pastemargin of about 4 mm in width on the balloon-fixing portion of the tube,there was coated an appropriate amount of the addition polymerizationtype silicone composition for adhesive use mentioned in Example 1. Theballoon tube and the tube were allowed to adhere to each other by aheat-treatment at 100° C. for 2 hr. To the other end of the tube wasallowed to adhere a branched connector connected with the fluid passagefor balloon expansion and the tube bore, with cyclohexane. At the end ofthe connector branch connecting with the fluid passage for balloonexpansion, there was equipped a check valve. At the portions of the tubein the vicinity of both ends of the balloon, there were opened two sideholes of 0.8 mm in diameter extending to the tube bore.

In conventional drainage tubes, there have been used polyethylene orsoft vinyl chloride resin tubes without balloon, or silicone rubbertubes with a silicone rubber balloon. The former tubes were rigid andcould easily be inserted up to a bile duct percutaneously andtranshepatically, however, have drawbacks in that there is no means forfilling the tubes inside the bile duct and the tubes tend to bedisplaced out of the body due to the constantly occurring respiratorylocomotion movement of liver and other reasons. The latter tubes can betightly fixed inside the bile duct by expanding the balloon inside thebile duct and pressing the inner wall of the bile duct, however, theyhave a limitation that the tube main body and the balloon must be of thesame material and, moreover, because the tube is a silicone rubber tubeof relatively small outside diameter and accordingly is very low inrigidity, they buckle at the body surface at the time of insertionmaking the insertion difficult.

The drainage tube with a balloon according to the present invention hassolved the drawbacks of the conventional drainage tubes. In the tube ofthe present invention, a flexible balloon is attached to a rigid tube;fixing inside the bile duct is conducted reliably; dislocation can beprevented; and tube insertion from the body surface is easy. Thus, thedrainage tube with a balloon of the present invention is an idealpercutaneous transhepatic cholangio drainage tube.

EXAMPLE 5

The following experiment was conducted to produce a multilayer sheet ofthe soft vinyl chloride resin type from which plasticizer is leached outin only a very small amount.

To 100 parts by weight of a vinyl chloride resin (SX-DH, manufactured bySUMITOMO CHEMICAL CO., LTD.) were added 40 parts by weight of dioctylphthalate, 0.03 part by weight (as metal) of a Ca type stabilizer, 0.03part by weight (as metal) of a Zn type stabilizer and 10 parts by weightof epoxidized soybean oil. They were kneaded at 190° C. for 7 min by theuse of a roll and then pressed at 200° C. for 3 min into a sheet of 1 mmin thickness. Separately, an ethylene-vinyl alcohol copolymer (Eval F,manufactured by KURARAY CO., LTD.) was extruded into a film of 50μthickness by the use of an extruder.

The above soft vinyl chloride resin sheet was cut into 10 cm×10 cmsquares. On one side of each square sheet, there was coated an additionpolymerization type silicone composition prepared by adding, to 100parts of a dimethylpolysiloxane having dimethylvinylsilyl groups at bothends of the molecular chain and having a viscosity of 18,000 cs at 25°C., 5 parts by weight of a polysiloxane consisting of 10 mole % of atrimethylsiloxane unit, 40 mole % of a dimethylsiloxaee unit and 50 mole% of a methylhydrogensiloxane unit, 20 parts by weight of silica and 0.2part by weight of an isopropyl alcohol solution of chloroplatinic acid(1% of platinum in solution), in a thickness of 50μ by the use of aspacer. Thereon was further placed the above prepared Eval film (cutinto a 10 cm×10 cm square), whereby a multilayer laminate A wasprepared. On the Eval film of another multilayer laminate A, there wascoated the above addition polymerization type silicone composition in athickness of 50μ, whereby a multilayer laminate B was prepared. Thesetwo laminates A and B were placed in an oven and heated at 100° C. for90 min, whereby soft vinyl chloride type multilayer laminates A and Bwere produced. These two laminates each had strong adhesion among layersand formed a complete integral body.

The multilayer laminates A and B as well as the above-mentioned softvinyl chloride resin sheet as Comparative Example were each cut into adisc shape of 7 cm diameter. In accordance with JIS L 0821, each discwas set at the backside of a lid of a 500 ml metal container so that thesoft vinyl chloride resin layer of the disc faced the backside of thelid. 100 ml of distilled water was placed in the metal container. Afterputting on the lid, the container was placed in a constant temperaturebath of 40° C. and was given a vibration at 3 Hz for a given length oftime, whereby the plasticizer, etc. contained in the soft vinyl chorideresin layer were allowed to dissolve out into water. Thereafter, eachextract was taken out and the amount of dioctyl phthalate in the extractwas measured by gas chromatography. The results are shown in Table 6.

                                      TABLE 6                                     __________________________________________________________________________                   Amount of dioctyl                                                             phthalate dissolved                                                           (μg/ml)                                                     Tested laminate or    40° C.                                                                      Trans-                                                                              Flexi-                                       sheet          40° C. 1 hr                                                                   10 hr                                                                              parency                                                                             bility                                       __________________________________________________________________________    Example Multilayer                                                                           11     38   o     o                                                    laminate A                                                                    Multilayer                                                                            1>    10   o     o                                                    laminate B                                                            Comparative                                                                           Soft vinyl                                                                           95     254  o     o                                            Example chloride                                                                      resin sheet                                                           __________________________________________________________________________

In order to investigate thrombus resistances of the outermost surfacesof the multilayer laminates A and B and of the surface of the soft vinylchloride resin sheet as Comparative Example, each laminate or sheet wascut into a 5 mm×5 mm square. The square laminate or sheet was attachedto the bottom of a glass-made flat Petri dish of 50 mm diameter by theuse of a double-coated adhesive tape so that the surface to be evaluatedof the laminate or sheet was directed upward. 5 ml of a dog's freshblood was poured into the dish and the blood was incubated at 37° C. for4 min. Then, the blood was gently removed from the dish with distilledwater. The dish was treated with a 1% aqueous glutaraldehyde solutionfor 2 hr, washed with distilled water and air-dried. Thereafter, thesurface of the laminate or sheet was observed by a scanning typeelectron microscope. The results are shown in Table 7.

                  TABLE 7                                                         ______________________________________                                                       Number of platelets attached per unit                          Tested laminate or                                                                           area (mm.sup.2)                                                sheet          (Observation by electron microscope)                           ______________________________________                                        Example  Multilayer                                                                              9.3 × 10.sup.4                                                laminate A                                                                    Multilayer                                                                              1.2 × 10.sup.5                                                laminate B                                                           Comparative                                                                            Soft vinyl                                                                              7.5 × 10.sup.5                                       Example  chloride                                                                      resin sheet                                                          ______________________________________                                    

What is claimed is:
 1. A multilayer laminate comprising a catheter and aballoon laminated into one integral body with an addition polymerizationtype silicone rubber composition (b) at a balloon-fixing portion of thecatheter, wherein one of the catheter and the balloon is composed of athermoplastic resin (a) selected from the group consisting of soft vinylchloride resins ( 1), olefin resins (2), urethane resins (3), andstyrene resins (4) and the other is composed of a material selected fromthe group consisting of soft vinyl chloride resins (1), olefin resins(2), urethane resins (3), styrene resins (4) and wherein the soft vinylchloride resins (1) are selected from the group consisting of vinylchloride homopolymer, a vinyl chloride-ethylene copolymer, a vinylchloride-vinyl acetate copolymer, a vinyl chloride-ethylene-vinylacetate terpolymer, a vinyl chloride-(meth)acrylate copolymer, and avinyl chloride-urethane copolymer; the olefin resins (2) are selectedfrom the group consisting of low density polyethylenes, medium densitypolyethylenes, high density polyethylenes, linear low densitypolyethylenes, polypropylenes, ethylene-propylene block copolymers,ethylene-propyllene random copolymers, ethylene-propylene-dieneterpolymers, ethylene-vinyl acetate copolymers, ethylene-vinyl alcoholcopolymers, ionomer resins, and polybutadienes; the urethane resins (3)are selected from the group consisting of crosslinking typepolyurethane, and thermoplastic polyurethane elastomers; the styreneresins (4) are selected from the group consisting of polystyrene,styrene-butadiene copolymers, styrene-acrylonitrile copolymers,styrene-methyl methacrylate copolymers, acrylonitrile-butadiene-styreneterpolymers, poly-methylstyrene and polydichlorostyrene; and saidsilicone rubber compositions (b) consists of a mixture of (i) apolysiloxane having vinyl groups represented by the formula (5),##STR7## wherein R₁, R₂, R₃, and R₄ may be the same or different and areeach a monovalent hydrocarbon group having 6 or fewer carbon atoms and mis a positive integer, (ii) an organohydrogenpolysiloxane represented bythe formula (6), ##STR8## wherein R₅, R₇, R₈, R₉ and R₁₀ may be the sameor different and are each a monovalent hydrocarbon group having 6 orfewer carbon atoms, two R₆ 's each are a hydrogen atom or a same ordifferent monovalent hydrocarbon group having 3 or fewer carbon atoms, nis an integer of 2 to 100 and l is an integer of 0 to 100, and (iii) aninorganic substance as reinforcing component, and the silicone rubbercomposition (b) is able to be converted into a solid elastomer whensubjected to addition polymerization in the presence of a platinumcatalyst and furthermore wherein the organohydrogenpolysiloxane (ii) hasat least two hydrogen atoms directly bonded to silicon atoms in eachmolecule, and is present in the composition (b) in an amount sufficientto provide 0.6 to six such hydrogen atoms per one vinyl group of thesilicone rubber composition.
 2. A multilayer laminate according to claim1, wherein the soft vinyl chloride resin (1) contains at least onestabilizer selected from the group consisting of higher fatty acid metalsoaps, organometal stabilizers and inorganic metal stabilizers, andwherein the metal of said at least one stabilizer is calcium, zinc,lead, barium, magnesium or aluminum.
 3. A multilayer laminate accordingto claim 1, wherein the addition polymerization type silicone rubbercomposition (b) further comprises, as components for improving itsbonding strength, at least one compound selected from the groupconsisting of epoxy compounds, carboxylic acid anhydrides, siloxanes andsilanes having an acryloylalkyl group represented by the formula:##STR9## wherein R is CH₃ or a hydrogen atom and n is an integer of 1 to3, and unsaturated hydrocarbon group-containing oxysilane compounds. 4.A multilayer laminate according to claim 1, wherein the surface of thethermoplastic resin (a) is subjected, prior to adhesion to said siliconerubber composition (b), to low temperature plasma treatment with anorganohydrogenpolysiloxane including at least 30 mole % of anorganohydrogensiloxane unit and the organohydrogenpolysiloxane (ii) inthe composition (b) is present in the composition (b) in an amountsufficient to provide 0.8 to 6 such hydrogen atoms per one vinyl groupof the silicone rubber composition.
 5. A multilayer laminate accordingto claim 1, wherein the thermoplastic resin (a) includes 0.1 to 10 partsby weight, per 100 parts by weight of the resin, of athermoplasticity-imparting resin having a mean polymerization degree of3 to 200 and at least one carbon-carbon double bond per threepolymerization units in the molecule, and the organohydrogenpolysiloxane(ii) in the composition (b) is present in the composition (b) in anamount sufficient to provide 0.8 to 6 such hydrogen atoms per one vinylgroup of the silicone rubber composition.
 6. A multilayer laminateaccording to claim 1, wherein the thermoplastic resin (a) includes 0.01to 10 parts by weight, per 100 parts by weight of the resin (a), of anoragnohydrogenpolysiloxane having at least 30 mole % of anorganohydrogensiloxane unit.
 7. A multilayer laminate according to claim1, wherein the organohydrogenpolysiloxane (ii) in the composition (b)contains at least one vinyl group.